CN112717939A - Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Process for preparing catalyst - Google Patents
Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Process for preparing catalyst Download PDFInfo
- Publication number
- CN112717939A CN112717939A CN202110012670.5A CN202110012670A CN112717939A CN 112717939 A CN112717939 A CN 112717939A CN 202110012670 A CN202110012670 A CN 202110012670A CN 112717939 A CN112717939 A CN 112717939A
- Authority
- CN
- China
- Prior art keywords
- zro
- white precipitate
- drying
- catalyst
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an emulsion Ni/ZrO2 catalyst for catalytic hydrogenation upgrading of caprylic acid, which relates to the technical field of catalysts and comprises the following steps: (1) dissolving zirconium propanol in propanol, dripping deionized water into the solution to generate a white precipitate, filtering the white precipitate until the white precipitate is not increased any more, and drying the white precipitate; (2) impregnation of Ni (NO)3)2Loading on white precipitate, calcining, and reducing to obtain Ni/ZrO2Powder; (3) Ni/ZrO2 under vacuum environment2Drying to completely remove water, and cooling to room temperature in a dryer; (4) mixing Ni/ZrO2Adding into dichloromethane, and adding C17H38Si, slowly stirring the solution uniformly, and then adding B (C)6F5)3Significant bubbles are generated; (5) after the reaction is carried out until no bubbles exist, washing the sample by using dichloromethane and hexane, washing away residual and physically adsorbed hydrosilane, and then drying the sample in a vacuum environment again to obtain the modified emulsion catalyst Ni/ZrO2。
Description
Technical Field
The invention relates to the technical field of biomass catalytic hydrogenation upgrading catalysts, in particular to emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2A method for preparing the catalyst.
Background
The excessive consumption of fossil fuels raises concerns about environmental issues and national energy safety, and thus, the demand for environmentally friendly and renewable alternative fuels is increasing. At present, biomass plays an increasingly important role in the chemical industry as an alternative renewable carbon source, and is one of promising renewable energy sources. However, direct utilization of biomass as a liquid fuel is not feasible because biomass has a high oxygen content, a low combustion heat value, poor chemical stability and strong corrosiveness, which all hinder practical use of the product as a renewable energy source. Therefore, the production of liquid fuel with high combustion heat value by catalytic hydrogenation upgrading of biomass will provide significant environmental, economic and strategic advantages for the future. The main biomass product obtained by co-pyrolysis of the wood chips and the plastics at the early stage is the octanoic acid, and the octanoic acid is subjected to catalytic hydrogenation to prepare fuels with high combustion heat values such as gasoline and the like, so that the method has extremely high economic value.
At present, octanoic acid is subjected to catalytic hydrogenation to prepare fuel with high combustion heat value such as gasoline, and if common Ni/ZrO is adopted2The catalyst carries out catalytic hydrogenation on the octanoic acid, and as can be seen from figure 1, the common Ni/ZrO2The catalytic hydrogenation activity to the caprylic acid is not high, the conversion rate of the caprylic acid is increased along with the increase of the temperature, and the conversion rate of the caprylic acid reaches the highest at 240 ℃, but the conversion rate is only 53.2%, the yield of heptane is also low, only 23.6% and the yield of octane is only 17.6%.
Disclosure of Invention
The invention aims to provide a method for preparing caprylic acidEmulsion Ni/ZrO upgraded by catalytic hydrogenation2The preparation method of the catalyst aims to solve the technical problems of low reaction conversion rate and low product yield in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an emulsion Ni/ZrO2 catalyst for catalytic hydrogenation upgrading of caprylic acid comprises the following steps:
(1) dissolving zirconium propanol in propanol, dripping deionized water into the solution to generate a white precipitate, filtering the white precipitate until the white precipitate is not increased any more, and drying the white precipitate;
(2) impregnation of Ni (NO)3)2Loading on white precipitate, calcining, and reducing to obtain Ni/ZrO2Powder;
(3) Ni/ZrO2 under vacuum environment2Drying to completely remove water, and cooling to room temperature in a dryer;
(4) mixing Ni/ZrO2Adding into dichloromethane, and adding C17H38Si, slowly stirring the solution uniformly, and then adding B (C)6F5)3Significant bubbles are generated;
(5) after the reaction is carried out until no bubbles exist, washing the sample by using dichloromethane and hexane, washing away residual and physically adsorbed hydrosilane, and then drying the sample in a vacuum environment again to obtain the modified emulsion catalyst Ni/ZrO2。
Preferably, in the step (1), the ratio of the added zirconium propanol, the added propanol and the added deionized water is as follows: 1 g: 10 ml: 2 ml.
Preferably, in the step (2), Ni (NO) is loaded3)2The calcination temperature of the white precipitate is about 450 ℃, the calcination time is 3-5 h, and the calcination gas is air.
Preferably, in step (2), the reduction reaction after calcination is carried out at a temperature of about 450 ℃ in the presence of H2Under the condition of reducing gas.
Preferably, in the step (3), the dryer is a vacuum oven, and the drying temperature is 200 ℃.
Preferably, in step (4), Ni/ZrO2Dichloromethane, C17H38The ratio of the added Si is as follows: 1g to 20-40 ml to 1-1.5 g.
Compared with the prior art, the invention has the following beneficial effects:
1. the emulsion provided by the invention is Ni/ZrO2The catalyst can form a layer of powdery film between the water-oil phase interfaces. Stirring at high speed to make the water phase form small liquid beads to be dispersed in the oil phase, and emulsion Ni/ZrO2The catalyst is attached to the aqueous phase beads, encapsulating the droplets, such that the emulsion Ni/ZrO2The catalyst can better contact reactants in a water-oil two-phase, so that the catalytic activity is improved;
2. the emulsion provided by the invention is Ni/ZrO2The catalyst has high dispersion degree in water and oil phases. Emulsion Ni/ZrO2The catalyst has high dispersity in the water-oil phase, better contacts reactants in the water-oil two-phase, and improves the catalytic activity;
3. the emulsion provided by the invention is Ni/ZrO2The catalyst has relatively low cost, the used raw material medicament is safe and easy to obtain, the process flow is convenient and fast, the operation is simple, the energy is saved, and the engineering popularization is facilitated.
Drawings
FIG. 1 is a view of conventional Ni/ZrO2A catalytic hydrogenation result diagram of the catalyst on the octanoic acid;
FIG. 2 is an emulsion Ni/ZrO2A catalytic hydrogenation result diagram of the catalyst on the octanoic acid;
FIG. 3 shows emulsion catalyst Ni/ZrO2Distribution pattern at water-oil phase interface.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
Example 1
The emulsion provided by the invention is Ni/ZrO2The catalyst is prepared by the following steps:
a) 10g of zirconium propoxide was dissolved in 100mL of propanol and 20mL of deionized water was added dropwise to the solution. A white precipitate was obtained by filtration and then dried in an oven at 80 ℃ for 6 hours.
b) Adding a certain amount of Ni (NO) by impregnation3)2Loaded on the above white precipitate. Then calcining at 450 deg.C for 4H in air, and finally calcining with H at 450 deg.C2Reduction for 2h to obtain Ni/ZrO2And (3) powder.
c) Drying with a vacuum oven at 200 deg.C with 1g of Ni/ZrO2Drying for 12h, completely removing water, and cooling to room temperature in a dryer.
d) Mixing Ni/ZrO230ml of methylene chloride and 5mmol of C were added17H38And (3) Si. Slowly stirring the solution uniformly, adding B (C)6F5)3，B(C6F5)3After the addition, hydrogen generation was clearly observed.
e) After the reaction is carried out for 20min, washing the sample by using dichloromethane and hexane, washing away residual and physically adsorbed hydrosilane, and then drying the sample in a vacuum oven again to obtain the modified emulsion catalyst Ni/ZrO with the Ni load of 5 wt%2The distribution of the catalyst on the water-oil phase interface is shown in figure 3, and the emulsion catalyst Ni/ZrO2Between the water-oil phase interfaces.
Using emulsion Ni/ZrO2Catalyst and conventional Ni/ZrO2The catalyst is used for catalytic hydrogenation of octanoic acid, and the hydrogenation experimental process is as follows:
the octanoic acid catalytic hydrogenation test was conducted in two 100mL batch autoclaves. 0.1g of an emulsion Ni/ZrO2 catalyst and 3g of octanoic acid were ultrasonically dispersed in a mixed solvent of 7.5mL of deionized water and 42.5mL of n-decane, and 0.1g of a conventional Ni/ZrO2 catalyst and 3g of octanoic acid were ultrasonically dispersed in a mixed solvent of 7.5mL of deionized water and 42.5mL of n-decane, and then the two solutions were transferred to two 100mL stainless steel autoclave reactors, respectively. Reactor H2Purging three times, discharging impurity gas, and then using H2The pressure was increased to 2MPa and the stirring rate was constant (200 rpm). The reactor was then heated to the desired reaction temperature and maintained for 2 h. After the reaction is finished, cooling the autoclave to room temperature,a liquid sample was taken and analyzed for conversion of phenol and yield of reaction product using a gas chromatograph of agilent GC 6820. Gas chromatography uses a (GsBP Inowax 30m by 0.32mm by 0.25m) capillary column to separate the different component compounds, and finally the components are analyzed with a Flame Ionization Detector (FID).
Ordinary Ni/ZrO2The catalytic hydrogenation result of the catalyst on the octanoic acid is shown in figure 1, emulsion Ni/ZrO2The catalytic hydrogenation result of the catalyst on octanoic acid is shown in figure 2, and common Ni/ZrO can be seen from figure 12The catalytic hydrogenation activity for octanoic acid is not high. The conversion of octanoic acid increased with increasing temperature, and at 240 ℃, the conversion of octanoic acid reached the highest, with a conversion of only 53.2%, the yield of heptane was also lower, only 23.6%, and the yield of octane was only 17.6%. As can be seen from FIG. 2, the emulsion catalyst Ni/ZrO2The activity of catalytic hydrogenation of the octanoic acid is improved. The conversion rate of the octanoic acid can reach 73.3 percent at 240 ℃, compared with the common Ni/ZrO2The octanoic acid conversion rate is improved by 20.1 percent. The yield of heptane is also improved to 50.9%. In aqueous-oil phase reaction systems, ordinary Ni/ZrO2Easily agglomerate in the aqueous phase, making it difficult for the oil phase reactants to reach the catalyst activity. And emulsion catalyst Ni/ZrO2The catalyst is dispersed on a water-oil phase interface, and can better contact with reactants to perform catalytic reaction through the dispersion of surface tension, so that the conversion rate is improved.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (6)
1. A preparation method of an emulsion Ni/ZrO2 catalyst for catalytic hydrogenation upgrading of caprylic acid is characterized by comprising the following steps:
(1) dissolving zirconium propanol in propanol, dripping deionized water into the solution to generate a white precipitate, filtering the white precipitate until the white precipitate is not increased any more, and drying the white precipitate;
(2) impregnation of Ni (NO)3)2Loading on white precipitate, calcining, and reducing to obtain Ni/ZrO2Powder;
(3) Ni/ZrO2 under vacuum environment2Drying to completely remove water, and cooling to room temperature in a dryer;
(4) mixing Ni/ZrO2Adding into dichloromethane, and adding C17H38Si, slowly stirring the solution uniformly, and then adding B (C)6F5)3Significant bubbles are generated;
(5) after the reaction is carried out until no bubbles exist, washing the sample by using dichloromethane and hexane, washing away residual and physically adsorbed hydrosilane, and then drying the sample in a vacuum environment again to obtain the modified emulsion catalyst Ni/ZrO2。
2. The method according to claim 1, wherein in the step (1), the ratio of the amounts of zirconium propanol, propanol and deionized water added is: 1 g: 10 ml: 2 ml.
3. The production method according to claim 1 or 2, wherein in the step (2), Ni (NO) is loaded3)2The calcination temperature of the white precipitate is about 450 ℃, the calcination time is 3-5 h, and the calcination gas is air.
4. The method according to claim 3, wherein in the step (2), the reduction reaction after calcination is carried out at a temperature of about 450 ℃ in the form of H2Under the condition of reducing gas.
5. The method according to claim 1 or 2, wherein in the step (3), the dryer is a vacuum oven and the drying temperature is 200 ℃.
6. The production method according to claim 1 or 2, wherein in the step (4), Ni/ZrO2Dichloro(s)Methane, C17H38The ratio of the added Si is as follows: 1g to 20-40 ml to 1-1.5 g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110012670.5A CN112717939B (en) | 2021-01-06 | 2021-01-06 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid 2 Process for preparing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110012670.5A CN112717939B (en) | 2021-01-06 | 2021-01-06 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid 2 Process for preparing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112717939A true CN112717939A (en) | 2021-04-30 |
| CN112717939B CN112717939B (en) | 2023-02-10 |
Family
ID=75589918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110012670.5A Active CN112717939B (en) | 2021-01-06 | 2021-01-06 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid 2 Process for preparing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112717939B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351213A (en) * | 2021-06-10 | 2021-09-07 | 中国船舶重工集团公司第七一九研究所 | Hollow spherical shell-shaped Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof |
| CN113477254A (en) * | 2021-06-10 | 2021-10-08 | 中国船舶重工集团公司第七一九研究所 | Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2808561A1 (en) * | 1977-02-28 | 1978-08-31 | Dow Chemical Co | METHOD FOR HYDROGENATING HYDROCARBON MATERIALS |
| CN1268394A (en) * | 2000-04-28 | 2000-10-04 | 清华大学 | Preparation method of catalyst for methane reforming reaction by using carbon dioxide |
| CN101209951A (en) * | 2006-12-28 | 2008-07-02 | 中国石油化工股份有限公司 | Catalytic hydrogenation method for olefin |
| CN101693203A (en) * | 2009-10-30 | 2010-04-14 | 清华大学 | Method for preparing Ni base catalyst for methane portion oxidation synthesis gas |
| CN105521785A (en) * | 2014-09-30 | 2016-04-27 | 中国石油化工股份有限公司 | Nickel/titanium dioxide catalyst and preparation method thereof, and synthetic gas preparation method |
| CN105536800A (en) * | 2015-12-04 | 2016-05-04 | 南昌大学 | Synthesis method of Ni/ZrO2 hydrogenation catalyst and application of catalyst in hydrogenation catalysis reaction |
| CN108435251A (en) * | 2018-03-19 | 2018-08-24 | 山西大学 | A kind of preparation method and applications of separable emulsion catalyst |
| CN109289932A (en) * | 2018-10-30 | 2019-02-01 | 中国石油大学(华东) | A kind of Ni-based high dispersive emulsion catalyst and its preparation method and application |
| CN109433211A (en) * | 2018-11-22 | 2019-03-08 | 东南大学 | A kind of preparation method of octanoic acid hydrogenation deoxidation catalyst |
| CN110227536A (en) * | 2019-05-28 | 2019-09-13 | 东南大学 | It is a kind of for the NiMoW/MCM-41 composite catalyst of sad hydrogenation deoxidation and its preparation and application |
-
2021
- 2021-01-06 CN CN202110012670.5A patent/CN112717939B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2808561A1 (en) * | 1977-02-28 | 1978-08-31 | Dow Chemical Co | METHOD FOR HYDROGENATING HYDROCARBON MATERIALS |
| CN1268394A (en) * | 2000-04-28 | 2000-10-04 | 清华大学 | Preparation method of catalyst for methane reforming reaction by using carbon dioxide |
| CN101209951A (en) * | 2006-12-28 | 2008-07-02 | 中国石油化工股份有限公司 | Catalytic hydrogenation method for olefin |
| CN101693203A (en) * | 2009-10-30 | 2010-04-14 | 清华大学 | Method for preparing Ni base catalyst for methane portion oxidation synthesis gas |
| CN105521785A (en) * | 2014-09-30 | 2016-04-27 | 中国石油化工股份有限公司 | Nickel/titanium dioxide catalyst and preparation method thereof, and synthetic gas preparation method |
| CN105536800A (en) * | 2015-12-04 | 2016-05-04 | 南昌大学 | Synthesis method of Ni/ZrO2 hydrogenation catalyst and application of catalyst in hydrogenation catalysis reaction |
| CN108435251A (en) * | 2018-03-19 | 2018-08-24 | 山西大学 | A kind of preparation method and applications of separable emulsion catalyst |
| CN109289932A (en) * | 2018-10-30 | 2019-02-01 | 中国石油大学(华东) | A kind of Ni-based high dispersive emulsion catalyst and its preparation method and application |
| CN109433211A (en) * | 2018-11-22 | 2019-03-08 | 东南大学 | A kind of preparation method of octanoic acid hydrogenation deoxidation catalyst |
| CN110227536A (en) * | 2019-05-28 | 2019-09-13 | 东南大学 | It is a kind of for the NiMoW/MCM-41 composite catalyst of sad hydrogenation deoxidation and its preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| HAO CHEN ET AL.: "Deoxygenation of octanoic acid catalyzed by hollow spherical Ni/ZrO2", 《APPLIED CATALYSIS A: GENERAL》 * |
| 单媛媛等: "Ru/NiAl-LDH-o-CNTs乳液催化剂的制备", 《新型炭材料》 * |
| 李朝晖等: "微乳液法制备纳米Ni-Cu/A12O3碳二选择加氢", 《石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351213A (en) * | 2021-06-10 | 2021-09-07 | 中国船舶重工集团公司第七一九研究所 | Hollow spherical shell-shaped Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof |
| CN113477254A (en) * | 2021-06-10 | 2021-10-08 | 中国船舶重工集团公司第七一九研究所 | Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof |
| CN113351213B (en) * | 2021-06-10 | 2023-06-02 | 中国船舶重工集团公司第七一九研究所 | Hollow sphere shell-shaped Ni/ZrO for octanoic acid catalytic hydrogenation upgrading 2 Catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112717939B (en) | 2023-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112717939B (en) | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid 2 Process for preparing catalyst | |
| CN105779036B (en) | A kind of method that stalk produces traffic oil used in fuel | |
| CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
| CN112657557B (en) | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol | |
| CN114573429A (en) | Preparation method of 2-methoxy-4 methylphenol based on selective hydrodeoxygenation of vanillin | |
| CN108530255A (en) | A method of conversion lignin is ethylbenzene | |
| CN106278822A (en) | A kind of cellulose two-step method prepares ethylene glycol and the method for 1,2-propylene glycol | |
| KR101305907B1 (en) | Method for preparing high-yield biofuel from guaiacol | |
| CN112718010B (en) | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of caprylic acid | |
| CN114410336B (en) | Method for directly preparing long-chain alkane based on biomass levulinic acid | |
| Wang et al. | Chromium oxide‐modified mesoporous zirconium dioxide: efficient heterogeneous catalyst for the synthesis of 5‐Hydroxymethylfurfural | |
| CN108187650A (en) | It is a kind of using coal slime charcoal as solid alkali biodiesel catalyst of carrier and preparation method thereof | |
| CN112898246A (en) | Method for preparing 5-ethoxy methyl furfural | |
| CN115850042B (en) | Method for preparing 2-pentanone by using platinum-based catalyst for 2-methyl furan hydrogenation | |
| CN114605214B (en) | Synthetic method of n-hexane | |
| CN117942995A (en) | Oxygen-enriched vacancy MoO for hydrodeoxygenation of biomass gas solid systemx/ZrO2Catalyst, preparation method and application | |
| CN110511123A (en) | A method of catalysis veratryl alcohol is converted into 3,4- dimethoxy-p | |
| CN112058306A (en) | High-activity supported bifunctional catalyst, preparation method and application thereof | |
| CN113351213B (en) | Hollow sphere shell-shaped Ni/ZrO for octanoic acid catalytic hydrogenation upgrading 2 Catalyst and preparation method thereof | |
| CN109718778A (en) | A kind of method that Ni base catalyst itaconic acid adds hydrogen to prepare dimethyl succinic acid | |
| CN112778088B (en) | Method for synchronously preparing acrylic acid and 1, 2-propylene glycol by using glycerol | |
| CN114805251A (en) | Method for preparing 2,5-dimethylfuran by using 5-chloromethyl furfural | |
| CN107083254A (en) | A kind of method that utilization γ valerolactones prepare liquid fuel | |
| CN111925286B (en) | Me (Me) 2 Method for synthesizing formic acid by N-C (=O) -R solvent autocatalysis | |
| CN106622217A (en) | Glycerol C-C bond breakage catalysis method adopting carbothermal reduction Ru-based catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |